Dyeing human hair



United States Patent ()ilfice Patented Feb. 20, 1968 3,369,970 DYEING HUMAN HAIR Terence P. McLaughlin, Twickenham and John B. Wilkinson, Hampton, England, assignors to Lever Brothers Company, New York, N.Y., a corporation of Maine No Drawing. Continuation-impart of application Ser. No. 486,222, Sept. 9, 1965. This application Nov. 10, 1966, Ser. No. 593,581 Claims priority, application Great Britain, Aug. 20, 1959, 28,459/ 59 3 Claims. (Cl. 167-88) ABSTRACT OF THE DISCLOSURE This specification is concerned with a hair dye composition which is a substantially anhydrous viscous mixture of a powdered basic dye and a water-immiscible 011.

This is a continuation-in-part of application Ser. No. 486,222 filed on Sept. 9, 1965, which in turn is a continuation of application Ser. No. 49,843 filed on Aug. 16, 1960. Both of the aforementioned applications are now abandoned.

This invention relates to the dyeing of human hair.

Hair dyeing with synthethic dyes is usually performed by applying either disperse dyes or the so-called oxida-.

tion dyes (which are oxidised to a dye proper while in contact with the hair) to the hair from an aqueous medium. However, oxidation dyes have the disadvantage that they are allergens, and have to be used with great care; and disperse dyes generally produce a hair colouration that tends to be rather easily removable by washing.

We have investigated the use of basic dyes for dyeing hair. Basic dyes are a well-known class of dyes which are used in dyeing wool and cotton and in which that part of the dye molecule which confers colour and fibre aflinity (substantivity) on the whole is a cation, in particular an ammonium, sulphonium or oxonium cation. Such dyes have marked afi'inity for human hair when applied to it from an aqueous medium, and can be used safely to produce a hair colouration which is generally of greater permanence on washing than that imparted by disperse dyes. Moreover, many basic dyes produce a hair colouration of intensity approaching that given by oxidation dyes.

However, there is serious diificulty in putting basic dyes into a form marketable as a hair dye composition. For if they are sold dry, either alone or admixed with another ingredient such as a thickener, they may badly stain the users fingers when he mixes the dry composition with the water that is required for the dyeing procedure; while if they are sold already mixed with part of or all the required water, the composition has too short a storage life to be acceptable, owing to the instability of basic dyes in the presence of water. Basic dyes have a marked tendency to change in the presence of water to non-substantive materials, through destruction of the cationic charge as a result of the fusion of a hydroxyl ion, OH, with the dye cation; and the rate of this change, although usually low in comparison with that of preparative reactions, is yet high enough to be serious in compositions which are required to be storable for an extended period. Moreover, the change is accelerated if the hair dye composition is formulated with a mildly alkaline-reacting water-soluble substance, such as borax or sodium carbonate, to improve uniformity of distribution of the dye along the length of the hair filaments during the actual dyeing procedure. Thus, many basic-dye-based aqueous hair dye compositions prepared with the use of sodium carbonate fade seriously within a week of their preparation.

We have now found that hair dye compositions of a form convenient for use and of good storage life can be obtained from a basic dye by mixing the powdered y with substantially water-immiscible oil or grease into the form of a viscous liquid or paste. (By grease is mean a semi-solid material which readily flows under applied pressure, as lubricating grease does.) The basic dye remains in solid form in the oil or grease medium, since such dyes are substantially insoluble in water-immiscible materials. Surprisingly enough, when the composition is eventually incorporated in the aqueous medium from which the dye will be transferred to the hair, and dyeing is performed in the usual manner, transfer of the dye to the hair is not appreciable hindered by the water-immiscible oil or grease.

The invention thus provides a hair dye composition in the form of a substantially anhydrous viscous liquid or paste comprising a powdered basic dye mixed with a water-immiscible oil or grease.

The oil (which is suitably of Redwood viscosity greater than about seconds at 70 F.) or grease medium employed should of course be one that is non-toxic. The use of a hydrocarbon as the water-immiscible medium is much to be preferred, although vegetable or animal oils or greases (whose molecules contain oxygen) can be used if an anti-oxidant or other stabiliser is also incorporated to inhibit the development of rancidity in them. Ordinary petroleum jelly is a suitable hydrocarbon grease; and suitable oils are parafiinic hydrocarbon oils such as refined light paraffin oil and medicinal parafiin.

Basic dyes, like disperse dyes and oxidation dyes, are applied to the hair from an aqueous medium in the presence of a surface-active agent, whose function is to reduce the natural water-repellency of hair and so facilitate intimate contact of the aqueous medium with the hair. It will usually be convenient to incorporate the surfaceactive agent in the composition itself, and for this purpose a cationic or non-ionic surface-active agent may be used. Anionic surface-active agents are not compatible with the basic dye. Suitable cationic surface-active agents are long chain alkyl quaternary ammonium salts, such as cetyltrimethylammonium bromide, tetradecyltrimethylammonium chloride, laurylpyridinium bromide, tetradecylpyridinium chloride and stearyldimethylbenzylammonium chloride; and suitable non-ionic surface-active agents are long chain alkanolamides, such as lauric acid diethanolamide, and the condensation products of ethylene oxide or propylene oxide with a compound containing a long chain alkyl group and an active hydrogen atom, for example, the condensation product of nonylphenol with from 10 to 15 molar proportions of ethylene oxide. Incorporating a surface-active agent in a composition containing an oil (liquid) as distinct from a grease (semi-solid) has the further advantage of reducing the tendency of the dye particles to partly separate out from the oil ingredient on prolonged storage.

The proportion of surface-active agent employed depends on whether the composition is intended to be applied direct to wetted hair or to be diluted with water immediately before application; a higher proportion will be required in the latter instance, in order to disperse the oil or grease medium in the larger volume of Water. In general, the surface-active agent suitably forms from 2 to 25% by Weight of the composition.

A thickener compatible with the dye is preferably incorporated in the composition, so that when the composition is brought into contact with water the aqueous mixture formed is sufficiently viscous to be worked about on the head without draining unduly quickly from it. Methyl cellulose is very satisfactory for the purpose. The proportion of thickener employed will be less when the composition is one intended for application direct to wetted hair than when the composition is to be diluted with water before being applied to the hair. In general, the thickener suitably forms from 1 to 25% by weight of the composition.

A mildly alkaline-reacting water-soluble substance can be incorporated in the composition, to improve distribution of the dye between the tips and roots of the hair during the dyeing procedure. Such substances are insoluble in the waterimmiscib1e oil or grease. Like the other ingredients of the composition, the alkaline-reacting substance should be substantially water-free, for even 1% of weight of water in the composition will normally serious- 13 afiect the dlyes stability. Anhydrous alkali metal carbonates, and anhydrous borax, are examples of suitable mildly alkaline-reacting water-soluble substances.

The amount of mildly alkaline-reacting substance employed is preferably such that a pH of 7 to about 10 is obtained when the composition is brought into contact with water in the dyeing procedure. Some basic dyes as commercially available contain acid fillers, which require to be neutralised; with these dyes it is usually convenient to employ an amount of alkaline-reacting substance equal in weight to that of the dye, as in Example 2 below, so as to ensure the obtaining of the preferred pH subsequently.

The composition can contain perfume, and also an inert filler to provide a suitable bulk. Suitable inert fillers are calcium carbonate, talc and anhydrous sodium sulphate.

.The powdered basic dye suitably forms from 2 to 40% by weight of the total composition, but concentrations well outside this range may be used, depending upon the condition and colour of the hair to be treated and on the intensity of colouration which it is desired to produce. The powdered basic dyes commercially available are generally useable direct (that is, without further subdivision) in preparing compositions according to the invention.

The invention can be applied to the formulation of hair dye compositions from a wide variety of basic dyes used either singly, or mixed with one another or with other dyes, particularly disperse dyes, according to the colouration which it is desired to impart to the hair. However, said dyes should not be included, for they are incompatible with basic dyes.

Suitable basic dyes, among others, are Meldolas Blue (Colour Index No. 51175), Ethyl Violet (Colour Index No. 42600), Malachite Green (Colour Index No. 42000), Para Rosaniline (Colour Index No. 42500), Rhodamine B (Colour Index No. 45170), Capri Blue GN (L) (Colour Index No. 51000), Methylene Blue (Colour Index No. 52015), Indolenine Yellow (Colour Index No. 48010), Crystal Violet (Colour Index 42555).

The compositions of the invention can be applied direct to wetted greasy hair, that is, without a preliminary washing to remove the grease.

The compositions of the invention are in general noncorrosive to metals, and accordingly those that are in paste form can be marketed in collapsible aluminum tubes having no protective internal coating. The liquid compositions can be marketed in bottles or in sachets of the usual kind.

The invention is illustrated by the following examples:

EXAMPLE 1 The following ingredients were mixed together in the stated weight proportions:

Meldolas Blue (No. 51175, The Colour Index,

2nd edition (1956), volume 3, page 3429) Anhydrous Borax 30 Refined parafiin oil 30 Cetyltrimethylammonium bromide 10 Methyl cellulose 14.5 Perfume 0.5

*The grade employed here and in Example 2 was water'- white, and had specific gravity 0.858 at 60 F. and Redwood viscosIi ties 120 to 130 seconds at 70 F., 65 to 70 seconds at 100 The composition thus formed was found to be substantially unfaded after a years storage in a closed container.

The paste composition was used as follows: 5 grams of the composition were mixed into a smooth paste with 42 grams of water, and the aqueous mixture (pH about 8) was applied in the usual manner to a head of greying Negro hair, on which it was allowed to remain for 20 minutes, The hair was then thoroughly washed ot remove surplus dye.

The hair was found to have acquired an intense blueblack shade. It had an attractive gloss, and its colouration was stable to washing.

EXAMPLE 2 The following ingredients were mixed together in the stated weight proportions:

Ethyl Violet (No. 42600, The Colour Index,

2nd edition (1956), volume 3, page 3360) 7 Anhydrous borax 35 Refined paraffin oil 33.5 Cetyltrimethylammonium bromide 10 Methyl cellulose 14 Perfume 0.5

This composition can be used in the manner described in Example 1. When applied to a head of greying hair for 20 minutes it produced an attractive amethyst shade.

What is claimed is:

1. A hair dye composition in the form of a viscous mixture comprising powdered basic dye, a water-immiscible paraflinic hydrocarbon oil of Redwood viscosity greater than about seconds at 70 F., a surface-active agent selected from the class consisting of cationic and non-ionic surface-active agents, and a mildly alkalinereacting water-soluble substance selected from the class consisting of anhydrous alkali metal carbonates and anhydrous borax, the composition containing about 2% to 40% by Weight of the basic dye and the basic dye being substantially insoluble in the water-immiscible medium, said composition being substantially anhydrous.

2. A hair dye composition according to claim 1, in which the oil is refined light paraffin oil.

3. A hair dye composition in the form of a viscous A References Cited UNITED STATES PATENTS 1,594,490 8/1926 Bertolet 894 1,996,391 4/1935 Straus 4459 X 2,087,597 7/1937 Gutzeit 4459 2,114,370 4/1938 Bickenheuser 167-58 2,306,863 12/1942 Bour 86 X 3,086,914 4/1963 Soloway -167-88 X FOREIGN PATENTS 723,290 1/ 1932 France.

OTHER REFERENCES Pharmaceutical Formulas, vol. I, The Chemist and Druggist, London, England, 1944, p. 681.

ALBERT T. MEYERS, Primary Examiner.

VERA C. CLARKE, Assistant Examiner. 

